Influence of salinity on permeability characteristics of marine sediments

Abstract

Laboratory tests were conducted on compacted marine sediments to study the effect of salt concentration of permeating fluid on its permeability characteristics. Deep sea sediment samples were collected from water depths varying from 3700 to 4500 m off Mauritius coast. Liquid limit and plasticity index varied widely from 45 to 75 and 10 to 35, respectively. Permeability was found at different void ratios with distilled water and 0.2, 0.4, and 0.8 N NaCl solutions as permeating fluid. It was found that permeability increases with an increase in salt concentration for a given void ratio. This is explained by diffused double layer theory. Also, the rate of increase in permeability decreases with increase in salt concentration. The effect of salt concentration seemed to be less at higher void ratios.     

Paragenesis of fluids under evaporates in the Volga-Ural Basin

To unravel the mystery of the relationship between evaporates, Ca–Cl brines and accumulations of oil and N₂ in the basins of ancient cratons, their N₂, CH₄ and He concentration ratios, as well as the isotopic composition (δ¹⁵N, δ¹³C and ³He/⁴He) were compared within the Volga-Ural basin. The study allowed subsalt fluids from Volga-Ural Basin to divide into two genetic groups. The first one is found within the basin's platform area. It includes Ca–Cl brines, high-viscosity heavy oil, bitumen and N₂, which has concentrations higher than that of CH₄ and positive values of δ¹⁵N. The second one is tied to the edge of the platform, the Ural Foredeep and Peri-Caspian Depression. In this group, only the oil and gas reservoirs, which have more CH₄ than N₂, and possibly negative values of δ¹⁵N, were discovered. Interaction of gas components in compared fluids indicates great role of degassing in the formation of their composition. It is suggested that the fluids of the first group (N₂ > CH₄) is what remains, and the second group (N₂ < CH₄) is what is disappears from the rocks during their metamorphism and degassing.     

Permeability measurements in mudrocks using gas-expansion methods on plug and crushed-rock samples

Permeability is an important parameter relative to the production of hydrocarbons in shale oil/gas plays; however, the measurement of permeability in these nano-to microdarcy rocks remains a challenge. Results from different methods or from different laboratories are not consistent, and reasons are not fully understood. In the present study, permeability is measured for both plug and crushed-rock samples with different plug diameter or crushed-sample particle size to systematically investigate the permeability measurement to better understand and apply the measured results. A modified gas-expansion (MGE) method, which can measure permeability for plug samples under confining pressures, was established and applied to several Eagle Ford and Barnett Shale (mudrock) samples. Permeability results from this method are in fair agreement with those from the pulse-decay method. The traditional Gas Research Institute (GRI) method was applied to crushed-rock Eagle Ford Shale samples. The results were comparable to reported permeability for an Eagle Ford Shale sample. Particle or plug size has significant influence on permeability measurement. In general, permeability increases with increasing particle or plug size. For crushed sample with GRI method, the reason of increasing permeability is related to the limitation of the GRI technique and the data analysis method. Estimate of the permeability based on Kozeny–Carman Equation was conducted, and the results were used to evaluate the GRI permeability measurement. Particle size of 2–4 mm (5–10 meshes) is considered as an appropriate size for GRI permeability measurement. For plug sample, larger permeability with larger plug diameter is most likely caused by the artificial fractures. Higher confining pressure can reduce the influence of the fractures, but cannot fully remove it. A range of permeability, defined by the GRI permeability with 2–4 mm particles as the lower boundary and permeability of 1-in plug under high confining pressure (>5000 psi) as the upper boundary, can be a more reliable measures to represent the shale matrix permeability. The range of the permeability also highlights the uncertainty in matrix permeability measurement for shale.     

Stable carbon isotopic ratios of CH4-CO2-bearing fluid inclusions in fracture-fill mineralization from the Lower Saxony Basin (Germany) - A tool for tracing gas sources and maturity

The stable carbon isotopic ratios (δ¹³C) of methane (CH₄) and carbon dioxide (CO₂) of gas-rich fluid inclusions hosted in fracture-fill mineralization from the southern part of the Lower Saxony Basin, Germany have been measured online using a crushing device interfaced to an isotopic ratio mass spectrometer (IRMS). The data reveal that CH₄ trapped in inclusions seems to be derived from different source rocks with different organic matter types. The δ¹³C values of CH₄ in inclusions in quartz hosted by Carboniferous rocks range between −25 and −19‰, suggesting high-maturity coals as the source of methane. Methane in fluid inclusions in minerals hosted by Mesozoic strata has more negative carbon isotope ratios (−45 to −31‰) and appears to represent primary cracking products from type II kerogens, i.e., marine shales. There is a positive correlation between increasing homogenization temperatures of aqueous fluid inclusions and less negative δ¹³C(CH₄) values of in co-genetic gas inclusions probably indicating different mtaturity of the potential source rocks at the time the fluids were released. The CO₂ isotopic composition of CH₄-CO₂-bearing inclusions shows slight negative or even positive δ¹³C values indicating an inorganic source (e.g., water-rock interaction and dissolution of detrital, marine calcite) for CO₂ in inclusions. We conclude that the δ¹³C isotopic ratios of CH₄-CO₂-bearing fluid inclusions can be used to trace migration pathways, sources of gases, and alteration processes. Furthermore, the δ¹³C values of methane can be used to estimate the maturity of the rocks from which it was sourced. Results presented here are further supported by organic geochemical analysis of surface bitumens which coexist with the gas inclusion-rich fracture-fill mineralization and confirm the isotopic interpretations with respect to fluid source, type and maturity.     

Evolution of petrophysical properties of oil shales during high-temperature compaction tests: Implications for petroleum expulsion

The transport properties of Permian to Miocene oil shales (Torbanite, Posidonia, Messel, Himmetoglu, and Condor) were studied using petrophysical and geochemical techniques. The aims of this study were to assess permeability of oil shales, evaluate the evolution of porosity, specific surface area and intergranular permeability during high temperature compaction tests and to verify the suitability of intergranular permeability for petroleum expulsion. Measured permeability coefficients for two samples were 0.72 × 10⁻²¹ m² for the Eocene Messel shale and 2.63 × 10⁻²¹ m² for the Lower Jurassic Posidonia shale from S. Germany, respectively. BET specific surface areas of the original samples ranged from 0.7 to 10.6 m²/g and decreased after compaction to values from 0.3 to 3.7 m²/g. Initial porosity values ranged from 7.6 to 20.1 % for pre-deformation and from 9.99 to 20.7 % for post-deformation samples. Porosity increased during the high-temperature compaction experiments due to petroleum generation and expulsion. Permeability coefficients estimated using the Kozeny–Carman equation varied from 6.97 × 10⁻²⁴ m² to 5.22 × 10⁻²¹ m² for pre-deformation and from 0.2 × 10⁻²¹ m² to 4.8 × 10⁻²¹ m² for post-deformation samples reflecting the evolution of their porosity and BET specific surface areas. Measured and calculated permeability were similar for the Messel shale whereas calculated permeability was two orders of magnitude lower for the Posidonia shale from S. Germany. Petroleum expulsion efficiencies under the experimental conditions ranged from 38.6% for the Torbanite to 96.2% for the Posidonia shale from S. Germany. They showed strong positive correlation with the petroleum generation index (R² = 0.91) and poor correlations with porosity (R² = 0.46), average pore throat diameters (R² = 0.22), and compaction (R² = 0.02). Estimated minimum pore-system saturations for petroleum expulsion during the experiments were 12% for the Torbanite and 30% for the Posidonia shale from N. Germany. Pore-system saturation determines whether expulsion occurs mainly through matrix or fracture permeability. For samples with saturation levels above 20%, fracture permeability dominated during the experiments. Evidence based on the measured permeability coefficients, expulsion flow rates, consideration of capillary displacement during generation-related pore invasion and the existence of transport porosity suggests that fracture permeability is the principal avenue of petroleum expulsion from source rocks. This conclusion is supported by microscopic observations.     

Authigenic barite nodules and carbonate concretions in the Upper Devonian shale succession of western New York – A record of variable methane flux during burial

Authigenic barite nodules associated with modestly ¹³C-depleted calcium carbonate concretions and ³⁴S-enriched pyrite at the bottom of the Upper Devonian Hanover Shale of western New York provide evidence of sulfate reduction coupled with anaerobic oxidation of methane (AOM). The methane, much of it biogenic in origin, may have diffused upward from Middle Devonian Marcellus Shale and perhaps the Upper Ordovician Utica Shale. Strong ³⁴S enrichment and high δ³⁴S/δ¹⁸O values of the barite nodules reflect: (1) substantial kinetic fractionation induced by microbial sulfate reduction perhaps intensified by a low seawater sulfate recharge rate and (2) upward delivery of Ba²⁺- and CH₄- bearing pore fluid sourced within underlying sulfate-depleted deposits. However, the association of authigenic calcium carbonate and barite in the same stratigraphic interval, especially the presence of barite overgrowths on carbonate concretions, is not consistent with what is known of AOM-related mineralization of a sediment column passing downward through the sulfate–methane transition (SMT). The documented early formation of authigenic carbonate followed by barite observed relations may reflect a diminished rate of methanogenesis and/or CH₄ supply. The tempered methane flux would have induced the SMT to descend the sediment column enabling barite to form within the same stratigraphic horizon that ¹³C-depleted calcium carbonate had most recently precipitated. Diminished methane flux may have been caused by burial-related passage of the organic-rich Marcellus Shale below the depth of peak biogenic methane generation and its replacement at that depth interval by organic-lean deposits of the upper part of the Hamilton Group. Subsidence of the SMT would have increased the preservation potential of authigenic barite. However, continued survival of the labile barite as it eventually moved through the SMT suggests that the underlying sulfate-depleted zone was strongly enriched in Ba²⁺.     

A laboratory study on capillary sealing efficiency of Iranian shale and anhydrite caprocks

Caprock has the most important role in the long term safety of formation gas storage. The caprocks trap fluid accumulated beneath, contribute to lateral migration of this fluid and impede its upward migration. The rapid upward passage of invasive plumes due to buoyancy pressure is prevented by capillary pressure within these seal rocks. In the present study, two main seal rocks, from the Zagros basin in the southwest of Iran, a shale core sample of Asmari formation and an anhydrite core sample of Gachsaran formation, were provided. Absolute permeabilities of shale and anhydrite cores, considering the Klinkenberg effect, were measured as 6.09 × 10⁻¹⁸ and 0.89 × 10⁻¹⁸ m², respectively. Capillary sealing efficiency of the cores was investigated using gas breakthrough experiments. To do so, two distinct techniques including step by step and residual capillary pressure approaches were performed, using carbon dioxide, nitrogen and methane gases at temperatures of 70 and 90 °C, under confining pressures in the range 24.13–37.92 MPa. In the first technique, it was found that capillary breakthrough pressure of the cores varies in the range from 2.76 to 34.34 MPa. Moreover, the measurements indicated that after capillary breakthrough, gas effective permeabilities lie in range 1.85 × 10⁻²¹ – 1.66 × 10⁻¹⁹ m². In the second technique, the minimum capillary displacement pressure of shale varied from 0.66 to 1.45 MPa with the maximum effective permeability around 7.76 × 10⁻²¹ – 6.69 × 10⁻²⁰ m². The results indicate that anhydrite caprock of the Gachsaran formation provides proper capillary sealing efficacy, suitable for long term storage of the injected CO₂ plumes, due to its higher capillary breakthrough pressure and lower gas effective permeability.     

Estimates of methane output from mud extrusions at the erosive convergent margin off Costa Rica

Four mud extrusions were investigated along the erosive subduction zone off Costa Rica. Active fluid seepage from these structures is indicated by chemosynthetic communities, authigenic carbonates and methane plumes in the water column. We estimate the methane output from the individual mud extrusions using two independent approaches. The first is based on the amount of CH₄ that becomes anaerobically oxidized in the sediment beneath areas covered by chemosynthetic communities, which ranges from 10⁴ to 10⁵ mol yr^− 1. The remaining portion of CH₄, which is released into the ocean, has been estimated to be 10²–10⁴ mol yr^− 1 per mud extrusion. The second approach estimates the amount of CH₄ discharging into the water column based on measurements of the near-bottom methane distribution and current velocities. This approach yields estimates between 10⁴–10⁵ mol yr⁻¹. The discrepancy of the amount of CH₄ emitted into the bottom water derived from the two approaches hints to methane seepage that cannot be accounted for by faunal growth, e.g. focused fluid emission through channels in sediments and fractures in carbonates. Extrapolated over the 48 mud extrusions discovered off Costa Rica, we estimate a CH₄ output of 20·10⁶ mol yr^− 1 from mud extrusions along this 350 km long section of the continental margin. These estimates of methane emissions at an erosional continental margin are considerably lower than those reported from mud extrusion at accretionary and passive margins. Almost half of the continental margins are described as non-accretionary. Assuming that the moderate emission of methane at the mud extrusions off Costa Rica are typical for this kind of setting, then global estimates of methane emissions from submarine mud extrusions, which are based on data of mud extrusions located at accretionary and passive continental margins, appear to be significantly too high.     

Continuous inline mapping of a dissolved methane plume at a blowout site in the Central North Sea UK using a membrane inlet mass spectrometer – Water column stratification impedes immediate methane release into the atmosphere

The dissolved methane (CH₄) plume rising from the crater of the blowout well 22/4b in the Central North Sea was mapped during stratified water column conditions. Geochemical surveys were conducted close to the seafloor at 80.3 m water depth, below the thermocline (61.1 m), and in the mixed surface layer (13.2 m) using membrane inlet mass spectrometry (MIMS) in combination with a towed CTD. Seawater was continuously transferred from the respective depth levels of the CTD to the MIMS by using an inline submersible pump. Close to the seafloor a well-defined CH₄ plume extended from the bubble release site ∼460 m towards the southwest. Along this distance CH₄ concentrations decreased from a maximum of 7872 nmol l⁻¹ to less than 250 nmol l⁻¹. Below the thermocline the well-defined CH₄ plume shape encountered at the seafloor was distorted and filaments were observed that extended towards the west and southwest in relation to current direction. Where the core of the bubble plume intersected this depth layer, footprints of high CH₄ concentrations of up to 17,900 nmol l⁻¹ were observed. In the mixed surface layer the CH₄ distribution with a maximum of up to 3654 nmol l⁻¹ was confined to a small patch of ∼60 m in diameter. The determination of the water column CH₄ inventories revealed that CH₄ transfer across the thermocline was strongly impeded as only ∼3% of the total water column inventory was located in the mixed surface layer. Best estimate of the CH₄ seabed release from the blowout was 1751 tons yr⁻¹. The fate of the trapped CH₄ (∼97%) that does not immediately reach the atmosphere remains speculative. In wintertime, when the water column becomes well mixed as well as during storm events newly released CH₄ and the trapped CH₄ pool can be transported rapidly to the sea surface and emitted into the atmosphere.     

Impacts of fossil anisotropy on the electric and permeability anisotropy of highly fossiliferous limestone: a case study

The Middle Eocene Lutetian Samalut formation is among the best examples of anisotropic fossiliferous rocks in Egypt, where the effect of the anisotropic Nummulite Gizehensis fossils on the petrophysical behavior can be traced. The Samalut formation has been sampled and studied at Wadi Feiran in SW Sinai. Petrographically, it is composed of two microfacies; Nummulitic packstone and Fusulinid mudstone. Tight cementation by micro to pseudosparite, aggrading neomorphism and compaction with increasing load pressure are the most important porosity-reducing factors. The anisotropy of the fossil content (λ_F), due to shape and orientation, and its effect on the petrophysical properties were assigned by measuring the lengths of the longest and shortest axes. Petrophysically, both microfacies are characterized by low porosity values (1.47 ≤ \({\emptyset _{{\text{He}}}}\) ≤ 5.29%). The formation resistivity factor (F) and permeability (k) were measured in the horizontal and vertical directions (parallel and perpendicular to the bedding plane, respectively). The studied samples are characterized by high to very high formation resistivity factor (190?≤?F?≤?8938) and relatively very low permeability (0.012?≤?k?≤?0.110 md). The studied samples are characterized by fair to medium electric anisotropy ‘λ_E’, which is attributed to a relatively medium to fair degree of electric foliation. It has been shown that, the fossil shape anisotropy and orientation ‘λ_F’ (1.5?≤?λ_F?≤?3.5) is the main contributor for the electric and permeability anisotropy that corrected for the same porosity value (1.61?≤?λ_EC?≤?2.25 and 1.03?≤?λ_kC?≤?2.04; respectively). Foliation of the studied microfacies has been contributed to the orientation of the fossil remains parallel to the bedding plane. The anisotropy degree is relatively greater for the Nummulitic packstone microfacies than that of the Fusulinid mudstone. The present study refers to the possible anisotropic effect of fossil content (due to shape and orientation) on the petrophysical properties of the studied rocks which may be extended to the anisotropy of reservoir rocks on the bedding scale.     

Laboratory testing of muds

The equipment and techniques used at H. R. Wallingford Limited (HR) for testing the properties of estuarine muds are described. Erosion under unidirectional currents is measured in an annular flume; a relationship between shear strength, τ_e, and density, ρ_d, is determined in the form: τ_e=a ρ_d ^b. Self-weight consolidation tests are run in settling columns, with density profiles and excess pore pressures measured during the consolidation period. An empirical relationship between effective stress, σ′, and density is determined in the form: σ′=a₀+a₁ρ+a₂ρ². Permeability, k, against density is determined in the form: log(k)=c₀+c₁ρ.     

Methane sources,sinks and fluxes in a temperate tidal Lagoon: The Arcachon lagoon (SW France)

The Arcachon lagoon is a 156 km² temperate mesotidal lagoon dominated by tidal flats (66% of the surface area). The methane (CH₄) sources, sinks and fluxes were estimated from water and pore water concentrations, from chamber flux measurements at the sediment–air (low tide), sediment–water and water–air (high tide) interfaces, and from potential oxidation and production rate measurements in sediments. CH₄ concentrations in waters were maximal (500–1000 nmol l⁻¹) in river waters and in tidal creeks at low tide, and minimal in the lagoon at high tide (<50 nmol l⁻¹). The major CH₄ sources are continental waters and the tidal pumping of sediment pore waters at low tide. Methanogenesis occurred in the tidal flat sediments, in which pore water concentrations were relatively high (2.5–8.0 μmol l⁻¹). Nevertheless, the sediment was a minor CH₄ source for the water column and the atmosphere because of a high degree of anaerobic and aerobic CH₄ oxidation in sediments. Atmospheric CH₄ fluxes at high and low tide were low compared to freshwater wetlands. Temperate tidal lagoons appear to be very minor contributor of CH₄ to global atmosphere and to open ocean.     

Depth profiles of volatile iodine and bromine-containing halocarbons in coastal Antarctic waters

Measurements of bromoform (CHBr₃), diiodomethane (CH₂I₂), chloroiodomethane (CH₂ICl) and bromoiodomethane (CH₂IBr) were made in the water column (5–100 m depth) of the Southern Ocean within 0–40 km of the Antarctic sea ice during the ANTXX1/2 transect of the German R/V Polarstern, at five locations between 70–72°S and 9–11°W in the Antarctic spring/summer of 2003–2004. Some of the profiles exhibited a very pronounced layer of surface sea-ice meltwater, as evidenced by salinity minima and temperature maxima, along with surface maxima in concentrations of CHBr₃, CH₂I₂, CH₂ICl and CH₂IBr. These results are consistent with in situ surface halocarbon production by ice algae liberated from the sea ice, although production within the sea ice followed by transport cannot be entirely ruled out. Additional sub-surface maxima in halocarbons occurred between 20 and 80 m. At a station further from shore and not affected by surface sea-ice meltwater, surface concentrations of CH₂I₂ were decreased whereas CH₂ICl concentrations were increased compared to the stations influenced by meltwater, consistent with photochemical conversion of CH₂I₂ to CH₂ICl, perhaps during upward mixing from a layer at  70 m enhanced in iodocarbons. Mean surface (5–10 m) water concentrations of halocarbons in these coastal Antarctic waters were 57 pmol l^− 1 CHBr₃ (range 44–78 pmol l^− 1), 4.2 pmol l^− 1 CH₂I₂ (range 1.7–8.2 pmol l^− 1), 0.8 pmol l^− 1 CH₂IBr (range 0.2–1.4 pmol l^− 1), and 0.7 pmol l^− 1 CH₂ICl (range 0.2–2.4 pmol l^− 1). Concurrent measurements in air suggested a sea-air flux of bromoform near the Antarctic coast of between 1 and 100 (mean 32.3, median 10.4) nmol m^− 2 day^− 1 and saturation anomalies of 557–1082% (mean 783%, median 733%), similar in magnitude to global shelf values. In surface samples affected by meltwater, CH₂I₂ fluxes ranged from 0.02 to 6.1 nmol m^− 2 day^− 1, with mean and median values of 1.9 and 1.1 nmol m^− 2 day^− 1, respectively.     

Spatial variation in shallow sediment methane sources and cycling on the Alaskan Beaufort Sea Shelf/Slope

The MITAS (Methane in the Arctic Shelf/Slope) expedition was conducted during September, 2009 onboard the U.S. Coast Guard Cutter (USCGC) Polar Sea (WAGB-11), on the Alaskan Shelf/Slope of the Beaufort Sea. Expedition goals were to investigate spatial variations in methane source(s), vertical methane flux in shallow sediments (<10 mbsf), and methane contributions to shallow sediment carbon cycling. Three nearshore to offshore transects were conducted across the slope at locations approximately 200 km apart in water column depths from 20 to 2100 m. Shallow sediments were collected by piston cores and vibracores and samples were analyzed for sediment headspace methane (CH₄), porewater sulfate (SO₄²⁻), chloride (Cl⁻), and dissolved inorganic carbon (DIC) concentrations, and CH₄ and DIC stable carbon isotope ratios (δ¹³C). Downward SO₄²⁻ diffusion rates estimated from sediment porewater SO₄²⁻ profiles were between −15.4 and −154.8 mmol m⁻² a⁻¹ and imply a large spatial variation in vertical CH₄ flux between transects in the study region. Lowest inferred CH₄ fluxes were estimated along the easternmost transect. Higher inferred CH₄ flux rates were observed in the western transects. Sediment headspace ${\mathrm{\delta }}^{13}{\text{C}}_{{\text{CH}}_4}$ values ranged from −138 to −48‰, suggesting strong differences in shallow sediment CH₄ cycling within and among sample locations. Measured porewater DIC concentrations ranged from 2.53 mM to 79.39 mM with δ¹³C_DIC values ranging from −36.4‰ to 5.1‰. Higher down-core DIC concentrations were observed to occur with lower δ¹³C where an increase in ${\mathrm{\delta }}^{13}{\text{C}}_{{\text{CH}}_4}$ was measured, indicating locations with active anaerobic oxidation of methane. Shallow core CH₄ production was inferred at the two western most transects (i.e. Thetis Island and Halkett) through observations of low ${\mathrm{\delta }}^{13}{\text{C}}_{{\text{CH}}_4}$ coupled with elevated DIC concentrations. At the easternmost Hammerhead transect and offshore locations, ${\mathrm{\delta }}^{13}{\text{C}}_{{\text{CH}}_4}$ and DIC concentrations were not coupled suggesting less rapid methane cycling. Results from the MITAS expedition represent one of the most comprehensive studies of methane source(s) and vertical methane flux in shallow sediments of the U.S. Alaskan Beaufort Shelf to date and show geospatially variable sediment methane flux that is highly influenced by the local geophysical environment.     

Chemical and isotopic evidence for the nature of the fluid in CH4-containing sediments of the Håkon Mosby Mud Volcano

The pore waters of CH₄-containing sediments of the Håkon Mosby Mud Volcano were rich in NH⁺ ₄, Br^-, and I^-; exhibited a high total alkalinity; but were poor in Cl^-and SO^2- ₄. The geological evidence and our data suggest that organic matter decomposition in preglacial or early interglacial sediments took place during early diagenesis (bacterial processes) and during metamorphism (thermogenic processes under the 3100-m-thick layer of glacial sediments), accompanied by mud volcano fluid generation. It is argued that the CH₄of the mud volcano sediments has a mixed, biogenic and thermogenic, origin.     

Nitrous oxide and methane in the Atlantic Ocean between 50°N and 52°S: Latitudinal distribution and sea-to-air flux

We discuss nitrous oxide (N₂O) and methane (CH₄) distributions in 49 vertical profiles covering the upper ∼300 m of the water column along two ∼13,500 km transects between ∼50°N and ∼52°S during the Atlantic Meridional Transect (AMT) programme (AMT cruises 12 and 13). Vertical N₂O profiles were amenable to analysis on the basis of common features coincident with Longhurst provinces. In contrast, CH₄ showed no such pattern. The most striking feature of the latitudinal depth distributions was a well-defined “plume” of exceptionally high N₂O concentrations coincident with very low levels of CH₄, located between ∼23.5°N and ∼23.5°S; this feature reflects the upwelling of deep waters containing N₂O derived from nitrification, as identified by an analysis of N₂O, apparent oxygen utilization (AOU) and NO₃⁻, and presumably depleted in CH₄ by bacterial oxidation. Sea-to-air emissions fluxes for a region equivalent to ∼42% of the Atlantic Ocean surface area were in the range 0.40–0.68 Tg N₂O yr⁻¹ and 0.81–1.43 Tg CH₄ yr⁻¹. Based on contemporary estimates of the global ocean source strengths of atmospheric N₂O and CH₄, the Atlantic Ocean could account for ∼6–15% and 4–13%, respectively, of these source totals. Given that the Atlantic Ocean accounts for around 20% of the global ocean surface, on unit area basis it appears that the Atlantic may be a slightly weaker source of atmospheric N₂O than other ocean regions but it could make a somewhat larger contribution to marine-derived atmospheric CH₄ than previously thought.     

A geochemical traverse along the “Sperchios Basin – Evoikos Gulf” graben (Central Greece): Origin and evolution of the emitted fluids

The studied area is a 130 km long fast spreading graben in Central Greece. Its complex geodynamical setting includes both the presence of a subduction slab at depth responsible for the recent (Quaternary) volcanic activity in the area and the western termination of a tectonic lineament of regional importance (the North-Anatolian fault). A high geothermal gradient is made evident by the presence of many thermal springs with temperatures from 19 to 82 °C, that discharge along the normal faults bordering the graben.In the period 2004–2012, 58 gas and 69 water samples were collected and their chemical and isotopic analysis revealed a wide range of compositions.Two main groups of thermal waters can be distinguished on the basis of their chemical composition. The first, represented by dilute waters (E.C. <0.6 mS/cm) of the westernmost sites, is characterised by the presence of CH₄-rich and mixed N₂–CH₄ gases. The second displays higher salinities (E.C. from 12 to 56 mS/cm) due to mixing with a modified marine component. Reservoir temperatures of 150–160 °C were estimated with cationic geothermometers at the easternmost sites.Along the graben, from west to east, the gas composition changes from CH₄- to CO₂-dominated through mixed N₂–CH₄ and N₂–CO₂ compositions, while at the same time the He isotopic composition goes from typical crustal values (<0.1 R/R_A) up to 0.87 R/R_A, showing in the easternmost sites a small (3–11%) but significant mantle input. The δ¹³C values of the CO₂-rich samples suggest a mixed origin (mantle and marine carbonates).     

Fractional distribution of HgCl2 and CH3HgCl in the intestine of a marine fish

HgCl₂, and to a lesser degree, CH₃HgCl, have been reported to inhibit the intestinal absorption of amino acids and sugars in marine fish.^1–6 The level of inhibition varied with the concentrations of the mercury compounds and the substrate as well as the fish species, seasons and the in vitro or in vivo techniques used in measurement. Comparison of rates derived from in vitro with those of in vivo procedures indicated that the mode of action of HgCl₂ was different from CH₃HgCl.^4,5 HgCl₂ appeared to act by binding to the amino acid transport channel proteins at the luminal interface and inhibited both the active and part of the facilitated diffusion components of transport (57 % inhibition at 20 ppm and 0·25 mm l-leucine.⁶ CH₃HgCl, at the same concentrations, did not exceed 40 % inhibition and appeared to involve mainly the active component as judged by: (a) the terminal tissue-to-medium concentration ratio (T/M) of leucine which was about one in these experiments, and (b) the fact that the Na-dependent component is 40 % of total transport (see Figs 10, 11 and 17 in Ref. 6). Comparison of in vitro (mucosa and serosa exposed) and in vivo (initially only mucosa exposed) inhibition of leucine uptake indicated that during short incubations the action of CH₃HgCl was permeability dependent while that of HgCl₂ was not.⁵ To further clarify the permeability and the mode of action of these compounds in leucine uptake inhibition, recently the distribution of ²⁰³HgCl₂ and CH₃²⁰³HgCl in the intestine of the toadfish (Opsanus tau) under in vitro and in vivo conditions were investigated. The results showed an initial rapid binding of both mercury compounds to the mucosal surface followed by a very slow tissue permeation in the case of HgCl₂ but a rapid permeation of CH₃HgCl. In the in vivo long term series HgCl₂ appeared to induce specific mucus secretion which protected leucine transport proteins against HgCl₂.     

中印度洋脊Edmond热液区成矿流体属性与来源:来自流体包裹体和He-Ar同位素的证据

To understand the source and nature of the ore-forming fluids of the Edmond hydrothermal field on the Central Indian Ridge, we studied the He-Ar isotope composition and fluid inclusions of the hydrothermal precipitates.Our results show that the sulfide samples contain noble gases He, Ne, Kr, and Xe with their abundances in between those of air-saturated water(ASW) and mid-ocean ridge basalt(MORB). The ~3He/~4He ratio varies from1.3 to 8.7 R_a(n=10, average: 5.1 R_a), whereas the ~(40)Ar/~(36) Ar ratio is from 285.3 to 314.7(n=10, average: 294.8). These results suggest that the He was derived from a mixture of MORB with variable amounts of seawater, but the Ar in the ore-forming fluids trapped in the sulfides is predominantly derived from seawater. The fluid inclusions of barite have a wide range of homogenization temperatures and salinities varying from 163°C to 260°C and 2.6 wt%to 8.5 wt% Na Cl equiv., respectively. It is suggested that the ore-forming fluids were produced by phase separation, which agreed with the present-day vent fluid study.